Process for the preparation of phosphonium sulfonate salts

ABSTRACT

A process for the preparation of a phosphonium sulfonate salt or phosphobetaine which comprises mixing in an aqueous medium at a temperature from above 0* C. to below 100* C. an inorganic sulfite with a cyclic or noncyclic ethylenically unsaturated quarternary phosphonium halide at a mole ratio of at least 3:1.

United States Patent Inventor Hill M. Priestley North Bergen, NJ.

Appl. No. 706,698

Filed Feb. 19, 1968 Patented Dec. 7, 1971 Assignee Lever BrothersCompany New York, N.Y.

PROCESS FOR THE PREPARATION OF PHOSPHONIUM SULFONATE SALTS 8 Claims, NoDrawings US. Cl 260/505 R Int. Cl ..C07c 143/24 Field of Search 260/505R,

E. Gilbert, Sulfonation and Related Reactions, pp. I48 15! N.Y., i965Primary Examiner-Howard T. Mars Assistant Examiner- Leo De CrescenteAll0rney Brumbaugh, Graves, Donohue & Raymond ABSTRACT: A process forthe preparation ofa phosphonium sulfonate salt or phosphobetaine whichcomprises mixing in an aqueous medium at a temperature from above 0 C.to below l00 C. an inorganic sulfite with a cyclic or noncyclicethylenically unsaturated quarternary phosphonium halide at a mole ratioof at least 3: 1v

PROCESS FOR THE PREPARATION OF PHOSPl-llONllUll/l SULFONATE SALTSPhosphonium sulfonate salts have been prepared heretofore by a varietyof methods, one of which is set forth in U.S. Pat. No. 2,828,332. Inaccordance with the present invention, there is provided a further andmore convenient process for the preparation of phosphonium sulfonatesalts or phosphobetaines which general class of compounds is known to beuseful as surfactants or as biological toxicants, for example, asmothproofing agents, fungicides, bactericides, herbicides,inseciticides, nematocides and the like.

lo the process of the present invention a cyclic or noncyclicethylenically unsaturated quaternary phosphonium halide is reacted withan inorganic sulfite. The reaction is conducted in an aqueous reactionmedium. The temperature for the reaction may range from above C. tobelow 100 C., for example, at room temperature. ln the reaction theinorganic sulfite and phosphonium halide are mixed together at a moleratio of at least about 3: 1.

Suitable inorganic sulfite reactants include ammonium sulfite, sodiumsulfite, potassium sulfite and the like.

The phosphonium halide reactants are exemplified by the compounds havingthe following structural formulas:

(Formula I!) wherein R is an alkyl radical having from ID to 18 carbonatoms, e.g., decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyland octadecyl radicals; R is an aryl radical having from 6 to 10 carbonatoms, e.g., phenyl, tolyl, benzyl, xylyl, dimethyl phenyl and naphthyl;R is an ethylenically unsaturated alkylene radical having three carbonatoms or such monoand di-methyl-substituted alkylene radicals, e.g., CH-CH CH-, -CH CHCH CH C(CH CH, and CH --C(CH C(CH R and R are the same ordifferent alkenyl radicals having from 2 to 18 carbon atoms, e.g.,propenyl, allyl, pentenyl, decenyl, tetradecenyl and octadecenyl; and Xis a halogen anion, erg chlorine, bromine and iodine.

Illustrative examples of the cyclic ethylenically unsaturated quaternaryphosphonium halide reactants having structural Formula I includeoctadecylphenyl-3methyl-3-phospholenium bromide;decyltolyl-Z-phospholenium chloride;heptadecylbenzyl-3,4-dimethyl-3phospholenium iodide;tridecylnaphthyl-3-methyl-2-phospholenium bromide; andtetradecylxylyl-2,3dimethyl-Z-phospholenium chloride.

Exemplary noncyclic ethylenically unsaturated quaternary phosphoniumhalide reactants having structural Formula ll includediallyldodecylphenylphosphonium bromide,dipropenylphenyltetradecylphosphonium bromide,didecenylhexadecyltolylphosphonium chloride,allyloctadecenyltridecylxylylphosphonium iodide,tetradecenyloctadecenylheptadecylnaphthylphosphonium chloride andpentyldecenyloctadecylbenzylphosphonium iodide.

The phosphonium sulfonate salts or phosphobetaines produced by theprocess of the invention have the following structural formulas, Formulalll compounds being derived from Formula I compounds and Formula 1V andV compounds being derived from Formula ll compounds:

R (l ormuln ill) (Formula lV) Fomi ula V) wherein R,, R and R,. are asdefined above; R 60 is the saturated alkylene sulfo anion derivative ofR e.g., CH, CH(SO 'CH CH -CH CH(S0 ),CH(SO )--CH Cl-l CH -CH(SOCl-l,-C(CH (S0 ')BCH CH CH(CH )CH(SO CH CH(CH;,)--C(CH3) (SO.-,')-and CH--C(CH ($0 CH(CH,,); R is the sulfoalkyl anion derivative of R i.e., thealkyl radical corresponding to the R alkenyl radical and bearing anegatively charged S0 portion; and R is a salt of the sulfoalkylderivative of R i.e., the alkyl radical corresponding to the R alkenylradical and bearing a neutral $0 M portion attached to carbon where M isthe cation corresponding to the cation of the inorganic sulfite reactantemployed.

Illustrative examples of the phosphonium sulfonate slat reactionproducts having structural Formula lll includeoctadecylphenyl-3-methyl-3phospholanium sulfonate,octadecylphenyl-3-methyl-4-phospholanium sulfonate,decyltolyl-2-phospholanium sulfonate, heptadecylbenzyl-3,4-dimethyl-3-phospholanium sulfonate, tridecylnaphthyl3-methyl-2-phospholanium sulfonate and tetradecylxylyl-2,3-dimethyl-Z-phospholanium sulfonate.

Exemplary phosphobetaine reaction products having the structural FormulalV include phenylallyl (2-sulfopropyl) dodecyl phosphobetaine,phenylallyl (Ii-sulfopropyl) dodecyl phosphobetaine and phenylprop enyl(2-sulfopropyl) tetradecyl phosphobetaine.

Typical phosphobetaine reaction products having the structural Formula Vinclude phenyl (Z-sodium sulfopropyl) (2- sulfopropyl) tetradecylphosphobetaine, phenyl (2-ammonium sulfopropyl) (2-sulfopropyl) dodecylphosphobetaine and the like.

Illustrative examples of the process of the invention are set forthbelow.

EXAMPLE 1 Preparation of (octadecyl) (phenyl) (Ii-methyl) phospholaniumsulfonates Equal molar quantities of octadecyl bromide and l-phenyl-3-methyl phospholene (prepared as shown in U.S. Pat. No. 2,853,5l8) wereheated at l05-l 15 C. for 2 hours in an atmosphere of nitrogen. One partof the crude phosphonium bromide (compound (1) above), namely,octadecylphenyl-IB- methyl-3-phospholenium bromide, was dissolved in 20parts of water, and this was added to 50 parts of 10 percent sodiumsulfite solution. A precipitate began to form in about five minutes. Themixture was allowed to stand at room temperature for 1 hour. The solidwas filtered, washed with a little distilled water and dried; The yieldwas 0.8 parts of octadecylphenyl-3'methy|=3-phospholanium sulfonate and0c tadecylphenyl-3 methyl-4-phospholanium sulfonate. lsomeric compounds(2) and (3) above I.

Analysis Calculated for C H ,,0;,PS: C 68.19; H l0.06; S 6.28. P

Found: C 67.55; H 10.1 I; S 6.99; P 5.60; 9.25.

The above isomeric phosphonium sulfonate salts or phosphobetaines wereprepared by the use of ammonium sulfite solution (pH 8.1 as shown below.

One part of the crude phosphonium bromide prepared above [Compound (1)abovelwas dissolved in 20 parts of water. and this was added to parts ofammonium sulfite dissolved in 25 parts of water. After a minute, aprecipitate formed. This was filtered off. washed with a little water,and dried. The elemental analysis is the same as that given above.

One part of diallyldodecylphenylphosphoniurn bromide [prepared byheating for 2 hours at l05l C., in a nitrogen atmosphere, equimolarquantities of diallylphenylphosphine (.lour. of the Chem. Soc., l947. p.1448) and dodecyl bromide] was dissolved in 10 parts of water. and thesolution added to parts of a saturated aqueous sodium sulfite solution.The mixture was stirred for 30 minutes at room temperature, and thenextracted with 40 parts of chloroform. Removal of the solvent left 0.94part ofa syrup, which was dispersible in water.

Analysis Calculated for C, H ,0 PS: C 65.42; H 9.38. Found: C 64.00; H9.26; Na 0.0 percent.

The above isomeric mixture of phenylallyl (2-sulfopropyl).

dodecyl phosphobetaine and phenylallyl (B-sulfopropyl) dodecylphosphobetaine was also prepared by the use of ammonium sulfite as shownbelow.

One part of the phosphonium bromide prepared above was dissolved in 5parts of water, and the solution added to a solu tion of 2 parts ofammonium sulfite in 5 parts of water. The precipitate which formed wasextracted with chloroform. Removal of the solvent left behind the crudeisomeric phosphobetaines. The elemental analysis is the same as thatgiven above.

EXAMPLE 3 Phosphobetaine from dipropenylphenyltetradecylphosphoniumbromide and aqueous sodium sulfite Dipropenylphenyltetradecylphosphoniumbromide was prepared by heating for 8 hours at l05-l l5 C. equimolarquantities of tetradecyl bromide and dipropenylphenyl hosphine (.lour.Chem. Soc. 1947, p. l448, using propeny bromide, Mg, tetrahydrofuran,and methyl iodide to initiate the Grignard). The crude phosphoniumbromide was treated with aqueous sodium sulfite, as described in example2. The phenyl (2-sodium sulfopropyl) (2-sulfopropyl) tetradecylphosphobetaine reaction 'product is soluble in water, and is neutral tolitmus.

Analysis Calculated For c .,H,..o..Ps,: C 54.40; H 8.10; Na 4.02 Found:C 54.68; H 8.2];Na 3.23 Various modifications and changes may be made inthe process of the invention by those skilled in the art withoutdeparting from the essence thereof and accordingly the invention is tobe limited only within the scope of the appended claims.

What is claimed is:

l. A process for the preparation of a phosphonium sulfonate salt whichcomprises mixing in an aqueous medium at a temperature from above 0 C.to below C. an inorganic sulfite selected from the group consisting ofammonium sulfite, sodium sulfite and potassium sulfite with anethylenically unsaturated quaternary phosphonium halide at a mole ratioof at least about 3:l. said phosphonium halide being selected from thegroup consisting of 2 and wherein R is an alkyl radical having from 10to 18 carbon atoms, R is an aryl radical having from 6 to 10 carbonatoms, R is an alkylene radical selected from the group consisting ofethylenically unsaturated alkylene radicals having three car bon atomsand such mono-and di-methyl-substituted alkylene radicals. R and R arealkenyl radicals having from 2 to l8 carbon atoms and X is a halogenanion selected from the group consisting ofchlorine, bromine and iodine.

2. The process as defined by claim I wherein the phosphonium halide isoctadecylphenyl-3-methyl-3-phospholenium bromide.

3. The process as defined by claim 1 wherein the phosphonium halide isdiallyldodecylphenylphosphonium bromide.

4. The process as defined by claim I wherein the phosphonium halide isdipropenylphenyltetradecylphosphonium bromide. l

5. The process as defined by claim 1 wherein the inorganic sulfite isammonium sulfite.

6. The process as defined by claim 1 wherein the inorganic sulfite issodium sulfite.

7. The process as defined by claim 1 wherein the inorganic sulfite ispotassium sulfite.

8. The process as defined by claim 1 wherein the temperature is roomtemperature.

l l k l *0

2. The process as defined by claim 1 wherein the phosphonium halide isoctadecylphenyl-3-methyl-3-phospholenium bromide.
 3. The process asdefined by claim 1 wherein the phosphonium halide isdiallyldodecylphenylphosphonium bromide.
 4. The process as defined byclaim 1 wherein the phosphonium halide isdipropenylphenyltetradecylphosphonium bromide.
 5. The process as definedby claim 1 wherein the inorganic sulfite is ammonium sulfite.
 6. Theprocess as defined by claim 1 wherein the inorganic sulfite is sodiumsulfite.
 7. The process as defined by claim 1 wherein the inorganicsulfite is potassium sulfite.
 8. The process as defined by claim 1wherein the temperature is room temperature.